Photographic developer composition



Patented Sept. 7, 1954 UNITED STATES OFFICE PHOTOGRAPHIC DEVELOPER COMPOSITION Thomas H. James and George A. Reynolds, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey N Drawing. Application August 3, 1953, Serial No. 372,169

18 Claims.

wherein R represents a hydroxy group when n represents a positive integer from 1 to 4 and. R represents a hydrogen atom when n represents a positive integer of from 2 to 4.

The following compounds are representative of this class of compounds with which our invention is concerned:

0=0 HOE 0 l-erythroascorbic acid Ht HO (DH C H2O H l-ascorbic acid OOH I (3H noon ll H0 HOCH fi-desoxy-l-ascorbic acid l-rhamnoascorbic acid HO OJ Ht HOOH HOCH l-fucoascorbic acid 0=C HON H 0 l HOCH H OH H OH

CHzOH d-glucoheptoascorbic acid Other compounds contemplated by the invention which have the above general structure are dand l-ascorbic acids, isoascorbic acid and other ascorbic acid analogs, e. g., sorboascorbic acid, w-lactoascorbic acid, maltoascorbic acid, 1- araboascorbic acid, l-glucoascorbic acid, d-galactoascorbic acid, l-guloascorbic acid, and. l-alloascorbic acid.

It will be apparent that the above compounds differ principally in the structure of the terminal group R-CH2--(CHOH) "-1- and some of the compounds are stereoisomers. Accordingly, herein and in the appended claims the stereoisomeric forms of the ascorbic acid compounds containing this group as shown by Pigman and Wolfrom, Advances in Carbohydrate Chemistry published by the Academic Press New York, 1946, pp. 79-106, are contemplated in the invention. Accordingly, the ascorbic acid analogs indicated are named to denote the particular sugar from which they can be synthesized. It will be apparent that the compounds are non-aromatic and contain the characteristic mononuclear heterocyclic ene-diol group and are not to be confused with the polyhydric aromatic compounds such as catechol or pyrogallic acid which show serious disadvantages such as strong tendency to form colored oxidation products in the development reaction or on contact with the oxygen in the air, which products discolor solutions and stain photographic materials.

We have discovered that the developing rate of developer solutions containing the above nonaromatic ene-diol compounds can be markedly accelerated by the addition to ene-diol silver halide developing compositions of 3-pyrazolidone compounds which themselves are only moderately active developing agents for silver halide. The

activity of the resulting developer solution containing both the ene-diol and the pyrazolidone is very much greater than would be expected from summing up the separate activities of these compounds. An added feature of these ene-diolpyrazolidone developer composition resides in the stability of the developing solutions. That is, 3- pyrazolidone compounds such as 1-phenyl-3- pyrazolidone are highly unstable in alkaline developer compositions free of a preservative and tend to darken and lose development activity quickly, particularly through aerial oxidation. On the other hand, when development is carried out with the B-pyrazolidone compounds in the presence of the ene-diol compounds, the latter function as preservatives and the developer is highly resistant to discoloration and loss of activity. Another advantageous characteristic of the ene-diol-pyrazolidone developer compositions is that the developers show little tendency for the formation of silver sludge or for the formation of dichroic stain on silver images. A further advantage is that since the ene-diol compounds are very effective preservatives for the pyrazolidone developing agents and are highly soluble in water, it is possible to prepare concentrated developer compositions more readily than in the case where a less soluble preservative such as sodium sulfite is used. A further characteristic of the ene-diol-pyrazolidone developer compositions of the invention resides in the fact that the compositions behave as strong surface latent image developers as opposed to internal latent image developers, as long as they are free of silver halide solvents such as sodium sulfite. taining 3-pyrazolidone compounds have been described in the literature but invariably they have been compounded so as to contain a silver halide solvent such as sodium sulfite as a preservative.

In order to convert such a developer composition to a surface'latent image developer, we have found it to be necessary to dispense with the silver halide solvent in the developer composition. However, as mentioned, the 3-pyrazolidone developers free of preservative are very unstable. When, according to our invention, the ene-diol compounds are incorporated into the 3-pyrazolidone developer compositions, the enediol compounds supply the required preservative effect and the surface latent image developer characteristics are maintained. Therefore, the fortuitous choice of 3-pyrazolidone compounds to accelerate the development rate of the enediol compounds has resulted in the latter compounds exerting a complementary preservative effect as well as providing a stable 3-pyrazolidone developer system which has surface latent image development characteristics and shows no tendency for physical development. For these reasons the developers of the invention are very That is, developer compositions conuseful in color development processes requiring a black-and-white developer.

An additional unexpected feature of the developers containing the 3-pyrazolidone and ascorbic acid compounds resides in the fact that similar developer compositions can be prepared, in which the pyrazolidone is replaced by a conventional developing agent, for example, a mixture of N-methyl-p-aminophenol and ascorbic acid, which compositions do not exhibit the mentioned development acceleration effect to anything like the same effect.

The 3-pyrazolidone developer compositions of the invention containing the above ene-diol compounds can be readily converted to internal latent image developer compositions by merely adding a silver halide solvent such as sodium thiosulfate thereto. The resultant internal latent image developer composition, by virtue of the presence of one of the mentioned ene-diol compounds, likewise possesses excellent keeping properties even in the absence of the usual sulfite preservative.

The 3-pyrazolidone silver halide developing agents employed in the developer compositions together with ascorbic acid and its analogs, have the general structure in which the R groups each represent various substituents such as hydrogen, alkyl or aryl groups, for example, R1 can be hydrogen or a group such as alkyl preferably containing from 1 to 4 carbon atoms, or an aryl group of the benzene or naphthalene series substituted or not, and R2, R3, R4 and R5 can be hydrogen atoms or alkyl as above or aryl such as phenyl.

The following compounds are representative of B-pyrazolidone silver halide developing agents which are useful in the developer compositions of the invention;

. 1-phenyl-3-pyrazolidone l-p-tolyl-3-pyrazolidone 5-phenyl-3-pyrazo1idone 5-methyl-3-pyrazolidone l-p-ohlorophenyl-B-pyrazolidone l-phenyl-5-phenyl-3-pyrazolidone 1-m-tolyl-3-pyrazolidone l-phenyl-5-methyl-3-pyrazolidone 1-p-tolyl-5-phenyl-3-pyrazolidone l-m-tolyl-3-pyrazolidone l-p-methoxyphenyl-3-pyrazolidone l-acetamidophenyl-3-pyrazo1idone 1 phenyl 2 acetyl 4,4 dimethyl 3 pyrazolidone 14. l-phenyl-4,4-dimethyl-3-pyrazolidone 15. 1 m aminophenyl 4 methyl 4 propyl 3 pyrazolidone 16. l o chlorophenyl 4 methyl 4 ethyl 3 pyrazolidone 1'7. 1 m acetamidophenyl 4,4 diethyl 3 pyrazolidone 18. l (p {3 hydroxyethylphenyl) 4,4 dimethyl 3 pyrazolidone 19. 1 p hydroxyphenyl 4,4 dimethyl 3 pyrazolidone 20. 1 p methoxyphenyl 4,4 diethyl 3 pyrazolidone 21. l-p-tolyl-4,4-dimethyl-B-pyrazolidone The 4,4-dialkyl-3-pyrazolidone compounds 13 to 23 and 26 above are particularly eflicacious for use in the developer compositions of our in-' vention inasmuch as they are more active developing agents than are compounds 1 to 12 which contain a single substituent or only hydrogen atoms in the 4-position of the pyrazolidone nucleus. The 4,4 dialkyl 3 pyrazolidone compounds are described and claimed in the Allen et a1. U. S. patent application Serial No. 372,148 filed concurrently herewith. The w-hydroxyalkyl- 3-pyrazolidones, for example, compounds 18 and 24 above, are also especially useful in concentrated formulas, in replenishers and in the presence of high salt concentrations where their increased solubility enables obtaining and holding adequate amounts of the pyrazolidone compound in solution. The compounds are described and claimed in the Allen et a1. U. S. Patent application Serial No. 372,148 filed concurrently herewith and in the Reynolds and Tinker U. S. Patent application Serial No. 372,167 filed concurrently. The Reynolds U. S. Patent application Serial No. 372,166 filed concurrently describes and claims developer compositions containing mixtures of the indicated ascorbic acid and ascorbic acid analogs containing an imino group, such as iminoglucoascorbic acid, in combination with the indicated 3-pyrazolidones.

Example 1 A solution of the following ingredients in 900 cc. water was prepared:

Grams 1 phenyl 3 pyrazolidone 0.5 d Ascorbic acid 3.0 Potassium bromide 1.2

Sodium metaborate was then added until a pH of 9.0 was attained and the solution was then made up to 1 liter with water. Exposed strips of a positive type film were then developed in (l) the above developer composition, (2) a glycine-carbonate surface latent image developer of the type described by G. W. W. Stevens, Phot. J. 82, 42-47 (1942) and (3) the following MQ latent image developer composition:

Water cc 500 N-methyl-p-aminophenol sulfate grams 2.2 Sodium sulfite, anhydrous do 96 Hydroquinone do 8.8 Sodium carbonate, monohydrate do 56 Potassium bromide do 5 Water to make liter 1 6 60 minutes development. That developer 3 strongly developed the internal latent image was established by the same test. Another advantage of developer 1 of the invention was that it maintained a much greater emulsion speed than did the other surface developer 2.

Example 2 Development of an exposed positive film was carried out using the 3-pyrazolidone-ascorbic acid developer of Example 1, the pH of which had been raised to 9.8. After 12 minutes development, the sensitometric curve of the film was found to be identical to that obtained in Example 1 by development for 24 minutes. The developer showed no signs of internal latent image development under these conditions.

Example 3 A pyrazolidone-ascorbic acid developer was developed in the N-methyl-p-aminophenol hydroquinone developer 3 of Example 1 for 12 minutes. As a result, the hydroquinone developer produced a slightly higher contrast image. When the development time was increased to 60 minutes, very little change in density or fog occurred with the developer of the invention.

The presence of internal latent image development was tested as in Example 1 but was found to be similarly absent with the pyrazolidoneascorbic acid developer and present with the N- methyl-p-aminophenol-hydroquinone developer. However, when 3 grams of sodium thiosulfate per liter were added to the pyrazolidone developer composition (pH 9.8 and containing 3.6 grams of bromide per liter), a stronger internal image development took place than when the same amount of hypo was added to the hydroquinone developer.

Example 4 A developing solution containing 1 gram of 1-phenyl-3-pyrazolidone and 10 grams of dascorbic acid per liter was prepared and adjusted to pH 10.0 with sodium carbonate solution. This developer was used for the development of a fast positive film and was found to give much faster development than the pyrazolidone-ascorbic acid developer compositions of the previous examples and there was no indication of internal latent image.

Example 5 The striking superadditivity obtained by combining the pyrazolidones and ene-diols, is shown in the following table. It is seen that the individual agents develop only weakly, but that when combined, they develop vigorously, producing images of high density.

These formulas all contained 25 grams of sodium sulfite and 25 grams of monohydrated sodium carbonate per liter, in addition to the indicated developing agents. In each case the pH of the formula was adjusted to 10.0 with acetic acid, to bring all solutions under parallel conditions.

The formulas compare the activity of the enediol ascorbic acid alone at an 0.02 molar concentration (3.5 grams per liter), of the pyrazolidone by itself, at 0.0025 molar concentration (0.4 to 0.5 gram per liter), and combinations of the 7 agents in these concentrations. Th activity was tested with a fine grain positive film given a step wedge exposure and developed for a series of times at 68 F. and with high agitation.

8 'd-ascorbic acids and either a 1-toly1-3-pyrazolidone such as 1-p-tolyl-3-pyrazolidone or l-pto'lyl-4,4-dimethyl-3-pyrazolidone, a l-(p-e-hydroxyalkylphenyl) 4,4 dialkyl 3 pyrazoli- Photographic Activity g f Developing Agents igggs Gamma 4 Min.

2 Min. .8 Min.

l-Phenyl-B-pyrazolidone.- 0. 41 0. 62 l-ascorbic acid+l-phenyl-3-pyrazolidone l. 79 1. 8 l-ascorbicacid l-escorbic acid l-p-(fi-hydroxyethyl 1.79 1. 83

phcnyl)-3-pyrazolidone. l-g- (fl-hydroxyethylphenyl) -3- pyrazoli- 0. 46 0. 60

one. l-ascorbic acld+l-phenyl-4,4-din1ethyl-3- 1. 79 1. 81

pyrazolidone. l-Phenyli,4-dimethyl-3-pyrazolldone 0. 38 0. 62

- No image.

Example 6 done such as 1- (p-fi-hydroxyethylphenyl) -4,4-

The following developer compositions are of particular use as negative developers for color films:

(1) Without sulfite: grams/liter Sodium hexametaphosphate 0.5 Sodium carbonate monohydrate 25.0 Potassium bromide 1.0 Potassium iodide 0.002 l-phenyl-ZB-pyrazolidone 1.0 Isoascorbic acid 10.0 l-phenyl-5-mercapto tetrazole 0.01 Water to make 1.0 liter.

-(2) With sulfite: grams/liter Sodium hexametaphosphate 0.5 Sodium :sulfite 40.0 Sodium carbonate monohydrate 25.0 Potassium bromide 1.0 Potassium iodide 0.002 .1-phenyl-3-pyrazolidone 1.0 Isoascorbic acid 10.0 1-phenyl-5-mercapto tetrazole 0.01

Water to makel.0 liter.

The developers of this example can be used in any of the well-known processes of color development where a black-and-white developer is required. The developers are especially useful in mixed grain color processes employing films such as disclosed in Marines et al. U. S. Patent 2,388,856 or in the Carroll et al. U. S. Patent 2,614,925, October 21, 1952, wherein, for example, is shown a two-layer film, one layer containing blue-sensitive silver halide, the other containing a mixture of green and red-sensitive silver halide grains. When the developers immediately above are used in the color process of the patents as the negative developer for such a film it is observed, particularly with the formula free of sulfite, that physical development efiects are minimized with the result that clean highlights free of stain are obtained and the color developed images have increased saturation because of decreased physical development in the negative developer of the invention.

Results similar to those shown in the above examples are obtained when developer compositions, either containing or free of silver halide solvents, are prepared from mixtures of at least one of the indicated B-pyrasolidone compounds and at least one of the indicated ascorbic acids or ascorbic acid analogs. Particularly valuable developer compositions in addition to those exemplified above are those containing l-, isoor dimethyl-ZZ-pyrazolidone, or a l-(p-w-hydroxyalkylphenyD-3-pyrazolidone such as l-(p-p-hydroxyethylphenyl) -3-pyrazolidone.

It will be understood that our invention as specified by the claims hereinafter, includes the mentioned developer compositions in either the liquid form exemplified above, or in the dry powder form such as packaged developer formulas suitable for dissolving in water to form a liquid developer. Such dry compositions include the mentioned 3pyrazolidone compounds, the enediol compound, and alkaline material such as sodium carbonate, caustic alkali or sodium perborate.

What we claim is:

1. A photographic developer composition comprising an alkaline material, a 3-pyrazolidone silver halide developing agent and a compound having the general structure wherein R represents a hydroxyl group when n represents a positive integer from 1 to 4 and R represents a hydrogen atom when n represents a positive integer from 2 to 4.

2. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of a S-pyrazolidone silver halide developing agent and a compound having the general structure HOH 4. Aphotographic developer composition comprising an aqueous alkaline solution containing .a mixture of a 3-pyrazolidone silver halide developin agent and a compound having the structure HOCH:CHOH-OHC=IC =0 OH OH 5. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of a 3-pyrazolidone silver halide developing agent and a compound having the structure 6. A photographic developer composition comprising an aqueous alkaline solution contain ing a mixture of a 3-pyrazolidone silver halide developing agent and a compound having the structure 7. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of a 3-pyrazolidone silver halide developing agent and ascorbic acid.

8. The developer composition of claim 2 wherein the designated B-pyrazolidone is 1-phenyl-3- pyrazolidone.

9. The developer composition of claim 2 wherein the designated 3-pyrazolidone is a 4,4-dialkyl- 3-pyrazolidone.

10. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of a l-tolyl-3-pyrazolidone and ascorbic acid.

11. A photographic developer composition comprising an aqueous alkaline solution contain- 1o ing a mixture of 1-p-toly1-4A-dimethyl-3- pyrazolidone and ascorbic acid.

12. A photographic developer composition com prising an aqueous alkaline solution containing a mixture of 1-phenyl-4,4-dimethyl-B-pyrazolidone and ascorbic acid.

13. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of l-p-(/3-hydroxyethylpheny1) -3- pyrazolidone and ascorbic acid.

14. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of 1-phenyl-3-pyrazolidone and ascorbic acid.

15. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of 1-p-tolyl-3-pyrazolidone and ascorbic acid.

16. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of a B-pyrazolidone silver halide developing agent and a compound of the class consisting of isoascorbic acid, l-ascorbic acid, (1- ascorbic acid, fi-desoxy-l-ascorbic acid, l-erythroascorbic acid, l-gluco-ascorbic acid, d-glucoascorbic acid, d-galactoascorbic acid, l-guloascorbic acid, l-alloascorbic acid, d-glucoheptoascorbic acid, l-rhamnoascorbic acid, l-fucoascorbic acid, l-araboascorbic acid, sorboascorbic acid, w-lactoascorbic acid and maltoascorbic acid.

17. The developer composition designated in claim 1 which has been adapted to the development of the internal latent image of exposed silver halide by the addition of a silver halide solvent.

18. The developer composition designated in claim 1 which is free of a silver halide solvent.

No references cited. 

1. A PHOTOGRAPHIC DEVELOPER COMPOSITION COMPRISING AN ALKALINE MATERIAL, A 3-PYRAZOLIDONE SILVER HALIDE DEVELOPING AGENT AND A COMPOUND HAVING THE GENERAL STRUCTURE 